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含能材料  2015 

N-羟甲基叔胺的乙酰解反应及其在DAPT合成TAT反应机理中的应用

DOI: 10.11943/j.issn.1006-9941.2015.11.008

Keywords: 乙酰解 N-羟甲基叔胺 N,N-二烷基乙酰胺 3,7-二乙酰基-1,3,5,7-四氮杂双环[3.3.1]壬烷(DAPT) 1,3,5,7-四乙酰基-1,3,5,7-四氮杂环辛烷(TAT) 反应机理 硝酸铵

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Abstract:

为研究3, 7-二乙酰基-1, 3, 5, 7-四氮杂双环[3.3.1]壬烷(DAPT)乙酰解制备1, 3, 5, 7-四乙酰基-1, 3, 5, 7-四氮杂环辛烷(TAT)的反应机理, 以仲胺为原料与甲醛进行缩合反应合成了N-羟甲基叔胺, 并在乙酸酐中研究其乙酰解反应。结果表明:N-羟甲基叔胺在进行乙酰化时, 反应发生在氮原子而不是氧原子, 脱去羟甲基得到相应的N-乙酰化产物。DAPT乙酰解先得到7-乙酰氧基亚甲基-1, 3, 5-三乙酰基-1, 3, 5, 7-四氮杂环辛烷, 再经水解、乙酰化得到TAT; 考察了硝酸铵在N-羟甲基叔胺乙酰解过程中的作用, 发现硝酸铵在乙酰解过程中参与反应, 释放的硝酸与仲胺反应生成硝酸盐, 抑制了乙酰化反应的进行; 加入硝酸铵后, 乙酰化收率降低了18%~41%

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